High napthenic content marine fuel compositions

ABSTRACT

Marine diesel fuel/fuel blending component compositions and fuel oil/fuel blending component compositions are provided that are derived from crude oils having high naphthenes to aromatics volume and/or weight ratios and a low sulfur content. In addition to having a high naphthenes to aromatics ratio, a low sulfur content, and a low but substantial content of aromatics, such fuels and/or fuel blending components can have a reduced or minimized carbon intensity relative to fuels derived from conventional sources. The unexpected ratio of naphthenes to aromatics contributes to the fuels and/or fuel blending components further having additional unexpected properties, including low density, low kinematic viscosity, and/or high energy density.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.63/028,688, filed on May 22, 2020, the entire contents of which areincorporated herein by reference.

FIELD

This disclosure relates to marine fuel compositions having highnaphthenic content and low aromatic content, such as marine fuel oils,marine gas oils, and methods for forming such fuel compositions.

BACKGROUND

Regulatory bodies continue to mandate decreasing sulfur levels intransportation fuels to reduce SOx emissions from fuel combustion. Onesuch example is the International Maritime Organization (IMO) mandate toreduce sulfur in marine fuel used in the open ocean to 5000 mg/kg orless, which took effect January 2020. Prior to this mandate (“IMO2020”)taking effect, marine fuels used near coastal areas known as EmissionControl Areas or ECAs were already required to have 1000 mg/kg or lesssulfur, or in select areas 500 mg/kg or less sulfur. Inland waterwayssuch as lakes or rivers can require even lower sulfur levels in linewith on-road diesel, such as 10 mg/kg or less, or 15 mg/kg or less.

Expanding mandates create a need for more volume of low sulfur fuels forconsumption by marine vessels. Typically the lower sulfur marine fuelsavailable on the market, especially the fuels with sulfur level at orbelow 1000 mg/kg, have been distillates. These distillate molecules arein high demand, as they are also needed for on-road use and otherapplications such as home heating. Typically the production of lowersulfur fuels, especially for coastal ECAs, requires desulfurization orblending with desulfurized components due to straight-run materialdistilled from crude oil having higher sulfur levels.

In addition to being energy intensive, the desulfurization processincreases the carbon intensity associated with marine fuelmanufacturing, as the heat for the desulfurization process is typicallyprovided by combustion of hydrocarbons. It would be desirable to developcompositions suitable for use as low sulfur marine fuels while alsoreducing or minimizing the amount of refinery processing associated withproduction of a marine fuel.

U.S. Pat. No. 8,999,011 describes vacuum gas oil fractions that can beused in fuel compositions such as fuel oils.

U.S. Patent Application Publication 2017/0183575 describes fuelcompositions formed during hydroprocessing of deasphalted oils forlubricant production.

U.S. Patent Application Publication 2019/0185772 describes variousmarine fuel compositions, including fuel oils formed using hydrotreatedvacuum resid fractions.

An article titled “Catalytic Solutions for Processing Shale Oils in theFCC” (www.digitalrefining.com, April 2014) describes bottoms fractionsderived from shale oils extracted from various sources, along withmethods for processing the bottoms fractions.

SUMMARY

In various aspects, marine fuels and/or fuel blending components areformed at least in part from fractions derived from selected crude oilshaving a low sulfur content and a high naphthenes to aromatics weightratio and/or volume ratio. The fractions derived from the selected crudeoils can have a low sulfur content, a high naphthenes to aromaticsweight ratio, and a low but substantial content of aromatics. Thefractions can be used as fuels or fuel blending components afterfractionation and/or after blending with one or more other fractions,such as renewable fractions. For fractions that are not exposed tohydroprocessing conditions, the fractions can have characteristics thatindicate a lack of hydroprocessing, such as a weight ratio of aliphaticsulfur to total sulfur of 0.2 or more and/or a weight ratio of basicnitrogen to total nitrogen of 0.2 or more.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows compositional information for various crude oils.

FIG. 2 shows compositional information for various crude oils.

FIG. 3 shows modeled compositional values for atmospheric residfractions.

FIG. 4 shows modeled compositional values for atmospheric residfractions.

FIG. 5 shows measured and modeled compositional values for distillatefractions.

FIG. 6 shows measured and modeled compositional values for distillatefractions.

FIG. 7 shows measured and modeled compositional values for distillatefractions.

FIG. 8 shows measured and modeled compositional values for distillatefractions.

FIG. 9 shows measured and modeled compositional values for distillatefractions.

FIG. 10 shows measured compositional values for vacuum gas oilfractions.

FIG. 11 shows measured compositional values for vacuum gas oilfractions.

FIG. 12 shows modeled compositional values for vacuum gas oil fractions.

FIG. 13 shows modeled compositional values for vacuum gas oil fractions.

FIG. 14 shows modeled compositional values for vacuum resid fractions.

FIG. 15 shows modeled compositional values for blends of atmosphericresids with distillates.

DETAILED DESCRIPTION

In various aspects, marine diesel fuel/fuel blending componentcompositions and fuel oil/fuel blending component compositions areprovided that include at least a portion of a crude oil fraction havinga low sulfur content and high weight ratio and/or volume ratio ofnaphthenes to aromatics. It has been discovered that such fractions canbe used to form fuels and/or fuel blending components that have areduced or minimized carbon intensity relative to fuels derived fromconventional sources. This reduced carbon intensity is provided based inpart on a combination of an unexpectedly low sulfur content, anunexpectedly high weight ratio and/or volume ratio of naphthenes toaromatics, and a low but substantial content of aromatics in thefractions derived from such crude oils. The unexpected ratio ofnaphthenes to aromatics contributes to the fractions further havingadditional unexpected properties, including low density, low kinematicviscosity, and/or high energy density. Based on this unexpectedcombination of features, the fractions can be suitable for production oflow carbon intensity fuels and/or fuel blending components with only areduced or minimized amount of processing. For example, distillation ofa select crude oil feed into appropriate fractions can be sufficient toform some fractions that are directly usable as marine fuel and/or fuelblending components, without needing to expose the fraction(s) tohydroprocessing conditions.

By reducing, minimizing, and/or eliminating processing at various stagesin the life cycle of a fuel and/or fuel blending component, a fuel orfuel blending component can be formed that has a reduced carbonintensity. In other words, due to this reduced or minimized processing,the net amount of CO₂ generation that is required to produce a fuel orfuel blending component and then use the resulting fuel can be reduced.

As an example, some selected shale oil fractions including a resid orbottoms portion of a shale crude can be used for production of lowcarbon intensity, low sulfur marine fuels, such as low sulfur fuel oils.In some aspects involving an atmospheric resid fraction, a reduced orminimized amount of processing is needed to form a marine fuel oil. Thisis due in part to the low density and kinematic viscosity of theatmospheric resid fraction, so that the specifications for density andkinematic viscosity can be satisfied without addition of a distillateboiling range flux. Because a distillate boiling range flux is notneeded, a fuel oil formed from a low carbon intensity atmospheric residfraction can have an unexpectedly high flash point. Additionally,hydroprocessing of the atmospheric resid fraction can be reduced,minimized, or eliminated due to the low sulfur content. By reducing orminimizing processing of the atmospheric resid fraction, in combinationwith reducing or minimizing the amount of blending with higher carbonintensity components, a low carbon intensity fuel oil can be formed.Such fuels can provide still further advantages based on the lownitrogen content, low n-heptane insolubles content, and/or low contentof micro carbon residue (MCR).

As another example, various blending components can be added to anatmospheric or vacuum resid fraction to form low carbon intensity marinefuels with unexpectedly high ratios of naphthenes to aromatics andunexpectedly low sulfur contents. In some aspects, at least a portion ofthe blend components can correspond to renewable blending components.

As yet another example, distillate fractions can be used can be used toform low carbon intensity marine distillate fuels with unexpectedly highratios of naphthenes to aromatics and unexpectedly low sulfur contents.In some aspects, at least a portion of the blend components cancorrespond to renewable blend components.

Recent legislation and/or regulations have created Emission ControlAreas in the coastal waters of various countries. In such EmissionControl Areas, marine vessels are constrained to have emissions thatcorrespond to the expected emissions from combustion of a low sulfurfuel oil having a sulfur content of roughly 0.1 wt % or less. Similarly,recent regulations have more generally set a global sulfur limit forfuel oil of 0.5 wt % or less. Currently, relatively few types of blendstocks are commercially available that satisfy this requirement. Inpart, the limited availability of suitable blend stocks for low sulfurfuel oils is based on the relatively high sulfur content of thetraditional feeds used for fuel oil production. The typical vacuum residfeeds used for fuel oil production often have sulfur contents of 2 wt %or more. Performing sufficient processing on such feeds to generate alow (or ultra-low) sulfur fuel oil is generally not economicallyfavorable. Additionally, such processing can substantially increase thecarbon intensity of the resulting fuel.

Crude oil production from shale oil formations has increasedsignificantly in the past 10 years. The properties of shale oil can varywidely between shale oil formations and even within a shale oilformation. It has been unexpectedly discovered that certain types ofshale oil fractions, having a high naphthene to aromatics ratio and alow sulfur content, can be beneficial for forming fuel and/or fuelblending products with reduced carbon intensity.

Due to the low sulfur content, in some aspects the selected crude oilfractions can be suitable for incorporation into low sulfur fuel oils orultra low sulfur fuel oils with only minimal processing other thandistillation. In some aspects, a crude oil fraction that is incorporatedinto a fuel or fuel blending product can correspond to a crude oilfraction that has not been hydroprocessed and/or that has not beencracked. In this discussion, a non-hydroprocessed fraction is defined asa fraction that has not been exposed to more than 10 psia of hydrogen inthe presence of a catalyst comprising a Group VI metal, a Group VIIImetal, a catalyst comprising a zeolitic framework, or a combinationthereof. In this discussion, a non-cracked fraction is defined as afraction that has not been exposed to a temperature of 400° C. or more.Optionally, hydroprocessing can be performed on a shale oil fraction tofacilitate use in an ultra-low sulfur fuel.

The lower carbon intensity of a fuel containing at least a portion of ahigh naphthenes to aromatic ratio, low sulfur fraction can be realizedby using a fuel containing at least a portion of such a high naphthenesto aromatic ratio, low sulfur fraction in any convenient type ofcombustion powered device. In some aspects, a fuel containing at least aportion of a high naphthenes to aromatic ratio, low sulfur fraction canbe used as fuel for a combustion engine in a ground transportationvehicle, a marine vessel, or another convenient type of vehicle. Stillother types of combustion devices can include generators, furnaces, andother combustion devices that are used to provide heat or power.

In addition to low sulfur content, the select crude oil fractions with ahigh ratio of naphthenes to aromatics can also have low nitrogen contentand low micro carbon residue content. These features can further reduceemissions associated with the shale oil fractions. For example, the lowmicro carbon residue content and/or the low aromatics content can reduceor minimize the amount of soot produced during combustion of the shaleoil fractions. The low nitrogen content can reduce or minimize thepotential for formation of NOx species during combustion of the shaleoil fractions.

In various aspects, a select crude oil fraction can be included as partof a fuel or fuel blending product. For convenience, unless otherwisespecified, it is understood that references to incorporation of a crudeoil fraction into a fuel also include incorporation of such a fractioninto a fuel blending product.

Definitions

All numerical values within the detailed description and the claimsherein are modified by “about” or “approximately” the indicated value,and take into account experimental error and variations that would beexpected by a person having ordinary skill in the art.

In this discussion, a shale crude oil is defined as a petroleum productwith a final boiling point greater than 550° C., or greater than 600°C., that is extracted from a shale petroleum source. A shale oilfraction is defined as a boiling range fraction derived from a shalecrude oil.

Unless otherwise specified, distillation points and boiling points canbe determined according to ASTM D2887. For samples that are notsusceptible to characterization using ASTM D2887, D7169 can be used. Itis noted that still other methods of boiling point characterization maybe provided in the examples. The values generated by such other methodsare believed to be indicative of the values that would be obtained underASTM D2887 and/or D7169. In this discussion, the distillate boilingrange is defined as 170° C. to 566° C. A distillate boiling rangefraction is defined as a fraction having a T10 distillation point of170° C. or more and a T90 distillation point of 566° C. or less. Anatmospheric resid is defined as a bottoms fraction having a T10distillation point of 149° C. or higher, or 350° C. or higher. In someaspects, an atmospheric resid can have a T90 distillation point of 550°C. or more, or 565° C. or more. A vacuum gas oil boiling range fractioncan have a T10 distillation point of 350° C. or higher and a T90distillation point of 535° C. or less. A vacuum resid is defined as abottoms fraction having a T10 distillation point of 500° C. or higher,or 565° C. or higher. A resid-containing fraction is defined as afraction that includes bottoms, and therefore can contain a vacuum residand/or an atmospheric resid. It is noted that the definitions fordistillate boiling range fraction, atmospheric resid, and vacuum residare based on boiling point only. Thus, a distillate boiling rangefraction or a resid-containing fraction (such as an atmosphericresid-containing fraction or a vacuum resid-containing fraction) caninclude components that did not pass through a distillation tower orother separation stage based on boiling point. A shale oil distillateboiling range fraction is defined as a shale oil fraction correspondingto the distillate boiling range. A shale oil atmospheric resid isdefined as a shale oil bottoms fraction corresponding to an atmosphericresid. A shale oil vacuum resid is defined as a shale oil bottomsfraction corresponding to a vacuum resid.

In this discussion, a hydroprocessed fraction refers to a hydrocarbonfraction and/or hydrocarbonaceous fraction that has been exposed to acatalyst having hydroprocessing activity in the presence of 300 kPa-a ormore of hydrogen at a temperature of 200° C. or more. Examples ofhydroprocessed fractions include hydroprocessed distillate fractions(i.e., a hydroprocessed fraction having the distillate boiling range)and hydroprocessed resid fractions (i.e., a hydroprocessed fractionhaving the resid boiling range). It is noted that a hydroprocessedfraction derived from a biological source, such as hydrotreatedvegetable oil, can correspond to a hydroprocessed distillate fractionand/or a hydroprocessed resid fraction, depending on the boiling rangeof the hydroprocessed fraction.

In this discussion, a cracked fraction refers to a hydrocarbon and/orhydrocarbonaceous fraction that is derived from the effluent of athermal cracking or catalytic cracking process. A cracked distillatefraction (having the distillate boiling range), such as a light cycleoil from a fluid catalytic cracking process, is an example of a crackedfraction.

In this discussion, renewable blending components can correspond torenewable distillate and/or vacuum gas oil and/or vacuum resid boilingrange components that are renewable based on one or more attributes.Some renewable blending components can correspond to components that arerenewable based on being of biological origin. Examples of renewableblending components of biological origin can include, but are notlimited to, fatty acid methyl esters (FAME), fatty acid alkyl esters,biodiesel, biomethanol, biologically derived dimethyl ether,oxymethylene ether, liquid derived from biomass, pyrolysis products frompyrolysis of biomass, products from gasification of biomass, andhydrotreated vegetable oil. Other renewable blending components cancorrespond to components that are renewable based on being extractedfrom a reservoir using renewable energy, such as petroleum extractedfrom a reservoir using an extraction method that is powered by renewableenergy, such as electricity generated by solar, wind, or hydroelectricpower. Still other renewable blending components can correspond toblending components that are made or processed using renewable energy,such as Fischer-Tropsch distillate that is formed using processes thatare powered by renewable energy, or conventional petroleum distillatethat is hydroprocessed/otherwise refinery processed using reactors thatare powered by renewable energy. Yet other renewable blending componentscan correspond to fuel blending components formed from recycling and/orprocessing of municipal solid waste, or another source ofcarbon-containing waste. An example of processing of waste is pyrolysisand/or gasification of waste, such as or gasification of municipal solidwaste.

More generally, high naphthenes to aromatics ratio, low sulfur contentfractions (such as a selected shale oil fraction) as described hereinmay be blended with any of the following and any combination thereof inorder to form a fuel and/or fuel blending component: low sulfur diesel(sulfur content of less than 500 wppm), ultra low sulfur diesel (sulfurcontent <10 or <15 ppmw), low sulfur gas oil, ultra low sulfur gasoil,low sulfur kerosene, ultra low sulfur kerosene, hydrotreated straightrun diesel, hydrotreated straight run gas oil, hydrotreated straight runkerosene, hydrotreated cycle oil, hydrotreated thermally cracked diesel,hydrotreated thermally cracked gas oil, hydrotreated thermally crackedkerosene, hydrotreated coker diesel, hydrotreated coker gas oil,hydrotreated coker kerosene, hydrocracker diesel, hydrocracker gas oil,hydrocracker kerosene, gas-to-liquid diesel, gas-to-liquid kerosene,gas-to-liquid vacuum gas oil, hydrotreated vegetable oil, fatty acidmethyl esters, non-hydrotreated straight-run diesel, non-hydrotreatedstraight-run kerosene, non-hydrotreated straight-run gas oil and anydistillates derived from low sulfur crude slates, gas-to-liquid wax, andother gas-to-liquid hydrocarbons, non-hydrotreated cycle oil,non-hydrotreated fluid catalytic cracking slurry oil, non-hydrotreatedpyrolysis gas oil, non-hydrotreated cracked light gas oil,non-hydrotreated cracked heavy gas oil, non-hydrotreated pyrolysis lightgas oil, non-hydrotreated pyrolysis heavy gas oil, non-hydrotreatedpyrolysis distillate (e.g., kerosene and/or diesel), non-hydrotreatedpyrolysis residue, non-hydrotreated thermally cracked residue,non-hydrotreated thermally cracked heavy distillate, non-hydrotreatedcoker heavy distillates, non-hydrotreated vacuum gas oil,non-hydrotreated coker diesel, non-hydrotreated coker gasoil,non-hydrotreated coker vacuum gas oil, non-hydrotreated thermallycracked vacuum gas oil, non-hydrotreated thermally cracked diesel,non-hydrotreated thermally cracked gas oil, hydrotreated fats or oilssuch as hydrotreated vegetable oil, hydrotreated tall oil, etc., fattyacid methyl ester, Group 1 slack waxes, lube oil aromatic extracts,deasphalted oil, atmospheric tower bottoms, vacuum tower bottoms, steamcracker tar, any residue materials derived from low sulfur crude slates,LSFO, RSFO, other LSFO/RSFO blend stocks.

Additionally, as needed, fuel or fuel blending component fractionsgenerated from high naphthene to aromatics ratio, low sulfur fractionsand/or other blendstocks may be additized with additives such as pourpoint improver, cetane improver, lubricity improver, etc. to improveproperties and/or meet local specifications.

With regard to characterizing properties of distillate boiling rangefractions and/or blends of such fractions with other components to formdistillate fuels, a variety of methods can be used. Density of a blendat 15° C. (kg/m³) can be determined according ASTM D4052. Sulfur (inwppm) can be determined according to ASTM D2622. Kinematic viscosity ateither 40° C. or 50° C. (in cSt) can be determined according to ASTMD445. Cetane index for a distillate fraction or a marine gas oil can becalculated according to ASTM D4737, Procedure A.

For various marine fuels, density (in kg/m³) can be determined accordingto ISO 3675. For marine fuel oils, sulfur (in wppm) can be determinedaccording to ISO 8754. For marine fuel oils, kinematic viscosity at 50°C. (in cSt) can be determined according ISO 3104. For marine fuel oils,pour point can be determined according to ISO 3016. For marine fueloils, sediment can be determined according to ISO 10307-2. CCAI(calculated carbon aromaticity index) can be determined accordingEquation F.1 in ISO 8217:2012. Micro carbon residue content can bedetermined according to ASTM D4530. The content of n-heptane insolublescan be determined according to ASTM D3279. Flash point can be determinedaccording to ASTM D93. The metals content can be determined according toASTM D8056. Nitrogen can be determined according to D4629 for lowerconcentrations and D5762 for higher concentrations, as appropriate.

With regard to determining paraffin, naphthene, and aromatics contents,supercritical fluid chromatography (SFC) was used. The characterizationwas performed using a commercial supercritical fluid chromatographsystem, and the methodology represents an expansion on the methodologydescribed in ASTM D5186 to allow for separate characterization ofparaffins and naphthenes. The expansion on the ASTM D5186 methodologywas enabled by using additional separation columns, to allow forresolution of naphthenes and paraffins. The system was equipped with thefollowing components: a high pressure pump for delivery of supercriticalcarbon dioxide mobile phase; temperature controlled column oven;auto-sampler with high pressure liquid injection valve for delivery ofsample material into mobile phase; flame ionization detector; mobilephase splitter (low dead volume tee); back pressure regulator to keepthe CO₂ in supercritical state; and a computer and data system forcontrol of components and recording of data signal. For analysis,approximately 75 milligrams of sample was diluted in 2 milliliters oftoluene and loaded in standard septum cap autosampler vials. The samplewas introduced based via the high pressure sampling valve. The SFCseparation was performed using multiple commercial silica packed columns(5 micron with either 60 or 30 angstrom pores) connected in series (250mm in length either 2 mm or 4 mm ID). Column temperature was heldtypically at 35 or 40° C. For analysis, the head pressure of columns wastypically 250 bar. Liquid CO₂ flow rates were typically 0.3 ml/minutefor 2 mm ID columns or 2.0 ml/minute for 4 mm ID columns. The SFC FIDsignal was integrated into paraffin and naphthenic regions. In additionto characterizing aromatics according to ASTM D5186, a supercriticalfluid chromatograph was used to analyze samples for split of totalparaffins and total naphthenes. A variety of standards employing typicalmolecular types can be used to calibrate the paraffin/naphthene splitfor quantification.

In this discussion, the term “paraffin” refers to a saturatedhydrocarbon chain. Thus, a paraffin is an alkane that does not include aring structure. The paraffin may be straight-chain or branched-chain andis considered to be a non-ring compound. “Paraffin” is intended toembrace all structural isomeric forms of paraffins.

In this discussion, the term “naphthene” refers to a cycloalkane (alsoknown as a cycloparaffin). Therefore, naphthenes correspond to saturatedring structures. The term naphthene encompasses single-ring naphthenesand multi-ring naphthenes. The multi-ring naphthenes may have two ormore rings, e.g., two-rings, three-rings, four-rings, five-rings,six-rings, seven-rings, eight-rings, nine-rings, and ten-rings. Therings may be fused and/or bridged. The naphthene can also includevarious side chains, such as one or more alkyl side chains of 1-10carbons.

In this discussion, the term “saturates” refers to all straight chain,branched, and cyclic paraffins. Thus, saturates correspond to acombination of paraffins and naphthenes.

In this discussion, the term “aromatic ring” means five or six atomsjoined in a ring structure wherein (i) at least four of the atoms joinedin the ring structure are carbon atoms and (ii) all of the carbon atomsjoined in the ring structure are aromatic carbon atoms. Therefore,aromatic rings correspond to unsaturated ring structures. Aromaticcarbons can be identified using, for example, ¹³C Nuclear MagneticResonance. Aromatic rings having atoms attached to the ring (e.g., oneor more heteroatoms, one or more carbon atoms, etc.) but which are notpart of the ring structure are within the scope of the term “aromaticring.” Additionally, it is noted that ring structures that include oneor more heteroatoms (such as sulfur, nitrogen, or oxygen) can correspondto an “aromatic ring” if the ring structure otherwise falls within thedefinition of an “aromatic ring”.

In this discussion, the term “non-aromatic ring” means four or morecarbon atoms joined in at least one ring structure wherein at least oneof the four or more carbon atoms in the ring structure is not anaromatic carbon atom. Non-aromatic rings having atoms attached to thering (e.g., one or more heteroatoms, one or more carbon atoms, etc.),but which are not part of the ring structure, are within the scope ofthe term “non-aromatic ring.”

In this discussion, the term “aromatics” refers to all compounds thatinclude at least one aromatic ring. Such compounds that include at leastone aromatic ring include compounds that have one or more hydrocarbonsubstituents. It is noted that a compound including at least onearomatic ring and at least one non-aromatic ring falls within thedefinition of the term “aromatics”.

It is noted that that some hydrocarbons present within a feed or productmay fall outside of the definitions for paraffins, naphthenes, andaromatics. For example, any alkenes that are not part of an aromaticcompound would fall outside of the above definitions. Similarly,non-aromatic compounds that include a heteroatom, such as sulfur,oxygen, or nitrogen, are not included in the definition of paraffins ornaphthenes.

Life Cycle Assessment and Carbon Intensity

Life cycle assessment (LCA) is a method of quantifying the“comprehensive” environmental impacts of manufactured products,including fuel products, from “cradle to grave”. Environmental impactsmay include greenhouse gas (GHG) emissions, freshwater impacts, or otherimpacts on the environment associated with the finished product. Thegeneral guidelines for LCA are specified in ISO 14040.

The “carbon intensity” of a fuel product (e.g. marine fuel oil or marinegas oil) is defined as the life cycle GHG emissions associated with thatproduct (g CO₂eq) relative to the energy content of that fuel product(MJ, LHV basis). Life cycle GHG emissions associated with fuel productsmust include GHG emissions associated with crude oil production; crudeoil transportation to a refinery; refining of the crude oil;transportation of the refined product to point of “fill”; and combustionof the fuel product.

GHG emissions associated with the stages of refined product life cyclesare assessed as follows.

(1) GHG emissions associated with drilling and well completion—includinghydraulic fracturing, shall be normalized with respect to the expectedultimate recovery of sales-quality crude oil from the well.

(2) All GHG emissions associated with the production of oil andassociated gas, including those associated with (a) operation ofartificial lift devices, (b) separation of oil, gas, and water, (c)crude oil stabilization and/or upgrading, among other GHG emissionssources shall be normalized with respect to the volume of oiltransferred to sales (e.g. to crude oil pipelines or rail). Thefractions of GHG emissions associated with production equipment to beallocated to crude oil, natural gas, and other hydrocarbon products(e.g. natural gas liquids) shall be specified accordance with ISO 14040.

(3) GHG emissions associated with rail, pipeline or other forms oftransportation between the production site(s) to the refinery shall benormalized with respect to the volume of crude oil transferred to therefinery.

(4) GHG emissions associated with the refining of crude oil to makeliquefied petroleum gas, gasoline, distillate fuels and other productsshall be assessed, explicitly accounting for the material flows withinthe refinery. These emissions shall be normalized with respect to thevolume of crude oil refined.

(5) All of the preceding GHG emissions shall be summed to obtain the“Well to refinery” (WTR) GHG intensity of crude oil (e.g. kg CO₂eq/bblcrude).

(6) For each refined product, the WTR GHG emissions shall be divided bythe product yield (barrels of refined product/barrels of crude), andthen multiplied by the share of refinery GHG specific to that refinedproduct. The allocation procedure shall be conducted in accordance withISO 14040. This procedure yields the WTR GHG intensity of each refinedproduct (e.g. kg CO₂eq/bbl gasoline).

(7) GHG emissions associated with rail, pipeline or other forms oftransportation between the refinery and point of fueling shall benormalized with respect to the volume of each refined product sold. Thesum of the GHG emissions associated with this step and the previous stepof this procedure is denoted the “Well to tank” (WTT) GHG intensity ofthe refined product.

(8) GHG emissions associated with the combustion of refined productsshall be assessed and normalized with respect to the volume of eachrefined product sold.

(9) The “carbon intensity” of each refined product is the sum of thecombustion emissions (kg CO₂eq/bbl) and the “WTT” emissions (kgCO₂eq/bbl) relative to the energy value of the refined product duringcombustion. Following the convention of the EPA Renewable Fuel Standard2, these emissions are expressed in terms of the low heating value (LHV)of the fuel, i.e. g CO₂eq/MJ refined product (LHV basis).

In this discussion, a low carbon intensity fuel or fuel blending productcorresponds to a fuel or fuel blending product that has reduced GHGemissions per unit of lower of heating value relative to a fuel or fuelblending product derived from a conventional petroleum source. In someaspects, the reduced GHG emissions can be due in part to reducedrefinery processing. For example, fractions that are not hydroprocessedfor sulfur removal have reduced well-to-refinery emissions relative tofractions that require hydroprocessing prior to incorporation into afuel. In various aspects, an unexpectedly high weight ratio ofnaphthenes to aromatics in a shale oil fraction can indicate a fractionwith reduced GHG emissions, and therefore a lower carbon intensity.

Another indicator of a low carbon intensity fuel can be an elevatedratio of aliphatic sulfur to total sulfur in a fuel or fuel blendingproduct. Aliphatic sulfur is generally easier to remove than other typesof sulfur present in a hydrocarbon fraction. In a hydrotreated fraction,the aliphatic sulfur will typically be removed almost entirely, whileother types of sulfur species will remain. The presence of increasedaliphatic sulfur in a product can indicate a lack of hydroprocessing forthe product. For example, a weight ratio of aliphatic sulfur to totalsulfur of 0.2 or more (or 0.3 or more, such as up to 0.8 or possiblystill higher) can indicate a product that has not been exposed tohydroprocessing conditions, while a weight ratio of aliphatic sulfur tototal sulfur of less than 0.1 can indicate a product that has beenhydroprocessed.

Still another indicator of a low carbon intensity fuel can be anelevated ratio of basic nitrogen to total nitrogen in a fuel or fuelblending product. Basic nitrogen is typically easier to remove byhydrotreatment. The presence of an increased amount of basic nitrogen ina product can therefore indicate a lack of hydroprocessing for theproduct. For example, a weight ratio of basic nitrogen to total nitrogenof 0.2 or more (or 0.3 or more, such as up to 0.8 or possibly stillhigher) can indicate a product that has not been exposed tohydroprocessing conditions, while a weight ratio of basic nitrogen tototal nitrogen of less than 0.2, or less than 0.1, can indicate aproduct that has been hydroprocessed.

Yet another indicator of a low carbon intensity fuel or fuel blendingproduct can be an elevated content of sodium and/or calcium in theproduct. Hydrotreating processes are generally effective for removal ofmetals during hydroprocessing, including removal of sodium and calcium.For a hydrotreated product, a typical sodium level is roughly 1 wppm orless, while a typical calcium level is roughly 1-7 wppm. By contrast,for resid fractions derived from shale crude oils with high naphthene toaromatic ratios, the sodium level without hydrotreatment is greater than5 wppm. For example, the sodium content without hydrotreatment can be 5wppm to 25 wppm, or 8 wppm to 25 wppm. Similarly, the calcium levelwithout hydrotreatment can be greater than 10 wppm, such as 10 wppm to25 wppm. The presence of such elevated levels of sodium and/or calciumin a product can indicate a lack of hydroprocessing.

Yet other ways of reducing carbon intensity for a hydrocarbon fractioncan be related to methods used for extraction of a crude oil. Forexample, carbon intensity for a fraction can be reduced by using solarpower, hydroelectric power, or another renewable energy source as thepower source for equipment involved in the extraction process, eitherduring drilling and well completion and/or during production of crudeoil. As another example, extracting crude oil from an extraction sitewithout using artificial lift can reduce the carbon intensity associatedwith a fuel.

Characterization of Shale Crude Oils and Shale Oil Fractions—General

Shale crude oils were obtained from a plurality of different shale oilextraction sources. Assays were performed on the shale crude oils todetermine various compositional characteristics and properties for theshale crude oils. The shale crude oils were also fractionated to formvarious types of fractions, including fractionation into atmosphericresid fractions, vacuum resid fractions, distillate fractions (includingkerosene, diesel, and vacuum gas oil boiling range fractions), andnaphtha fractions. Various types of characterization and/or assays werealso performed on these additional fractions.

The characterization of the shale crude oils and/or crude oil fractionsincluded a variety of procedures that were used to generate data. Forexample, data for boiling ranges and fractional distillation points wasgenerated using methods similar to compositional or pseudo compositionalanalysis such as ASTM D2887. For compositional features, such as theamounts of paraffins, isoparaffins, olefins, naphthenes, and/oraromatics in a crude oil and/or crude oil fraction, data was generatedusing analytical techniques such as high pressure liquid chromatography(HPLC) and/or gas chromatography-mass spectrometry (GC-MS). Data relatedto pour point was generated using methods similar to ASTM D97. Datarelated to cloud point was generated using methods similar to ASTM D2500and/or ASTM D5773. Data related to flash point was generated based onvolatility calculations. Data related to sulfur content and nitrogencontent of a crude oil and/or crude oil fraction was generated usingmethods similar to ASTMD2622, ASTM D4294, ASTM D5443, ASTM D4629, and/orASTM D5762. Data related to carbon content and/or hydrogen content wascalculated based on the compositional analysis. Data related to density(such as density at 15° C.) was generated using methods similar to ASTMD1298 and/or ASTM D4052. Data related to kinematic viscosity (such askinematic viscosity at 40° C. or 50° C.) was generated using methodssimilar to ASTM D445 and/or ASTM D7042. Data related to micro carbonresidue (MCR) content was generated using methods similar to ASTM D189and/or ASTM D4530. Data related to cetane index was calculated fromfractional distillation using techniques similar to those represented inthe American Petroleum Institute Technical Data Book. Data related toacid number was generated using methods similar to ASTM D664, ASTMD3242, ASTM D8045.

The data and other measured values for the shale crude oils and shaleoil fractions were then incorporated into an existing data library ofother representative conventional and non-conventional crude oils foruse in an empirical model. The empirical model was used to providepredictions for compositional characteristics and properties for someadditional shale oil fractions that were not directly characterizedexperimentally. In this discussion, data values provided by thisempirical model will be described as modeled data. In this discussion,data values that are not otherwise labeled as modeled data correspond tomeasured values and/or values that can be directly derived from measuredvalues.

FIGS. 1 and 2 show examples of the unexpected combinations of propertiesfor shale crude oils that have a high weight ratio and/or volume ratioof naphthenes to aromatics. In FIG. 1, both the weight ratio and thevolume ratio of naphthenes to aromatics is shown for five shale crudeoils relative to the weight/volume percentage of paraffins in the shalecrude oil. The top plot in FIG. 1 shows the weight ratio of naphthenesto aromatics, while the bottom plot shows the volume ratio. A pluralityof other representative conventional crudes are also shown in FIG. 1 forcomparison. As shown in FIG. 1, the selected shale crude oils describedherein have a paraffin content of greater than 40 wt % while also havinga weight ratio of naphthenes to aromatics of 1.8 or more. Similarly, asshown in FIG. 1, the selected shale crude oils described herein have aparaffin content of greater than 40 vol % while also having a weightratio of naphthenes to aromatics of 2.0 or more. By contrast, none ofthe conventional crude oils shown in FIG. 1 have a similar combinationof a paraffin content of greater than 40 wt % and a weight ratio ofnaphthenes to aromatics of 1.8 or more, or a combination of paraffincontent of greater than 40 vol % and a weight ratio of naphthenes toaromatics of 2.0 or more. It has been discovered that this unexpectedcombination of naphthenes to aromatics ratio and paraffin content ispresent throughout various fractions that can be derived from suchselected crude oils.

In FIG. 2, both the volume ratio and weight ratio of naphthenes toaromatics is shown for the five shale crude oils in FIG. 1 relative tothe weight of sulfur in the crude. The sulfur content of the crude inFIG. 2 is plotted on a logarithmic scale. The top plot in FIG. 2 showsthe weight ratio of naphthenes to aromatics, while the bottom plot showsthe volume ratio. The plurality of other representative conventionalcrude oils are also shown for comparison. As shown in FIG. 2, theselected shale crude oils have naphthene to aromatic volume ratios of2.0 or more, while all of the conventional crude oils have naphthene toaromatic volume ratios below 1.8. Similarly, as shown in FIG. 2, theselected shale crude oils have naphthene to aromatic weight ratios of1.8 or more, while all of the conventional crude oils have naphthene toaromatic weight ratios below 1.6. Additionally, the selected shale crudeoils have a sulfur content of roughly 0.1 wt % or less, while all of theconventional crude oils shown in FIG. 2 have a sulfur content of greaterthan 0.2 wt %. It has been discovered that this unexpected combinationof high naphthene to aromatics ratio and low sulfur is present withinvarious fractions that can be derived from such selected crude oils.This unexpected combination of properties contributes to the ability toproduce low carbon intensity fuels from shale oil fractions and/orblends of shale oil fractions derived from the shale crude oils.

It is noted that due to the difference in density between naphthenes andaromatics, the naphthenes to aromatics volume ratios shown in FIGS. 1and 2 are roughly 10%-12% greater than the naphthenes to aromaticsweight ratios in FIGS. 1 and 2. It is believed that this difference isalso present for the various other fractions described herein.

Characterization of Shale Oil Fractions—Atmospheric Resids andCorresponding Fuel Oils

In some aspects, an atmospheric resid fraction of a shale oil asdescribed herein or a fraction including both distillate and atmosphericresid can be used as a marine fuel oil or as a blending component for amarine fuel oil. The combination of low sulfur, high naphthene toaromatics ratio, low density, and low kinematic viscosity can allow anatmospheric resid fraction to be used as a marine fuel oil with reducedor minimized processing, such as possibly using the fraction as a fueloil after distillation without further processing.

FIG. 3 shows modeled data for atmospheric resid fractions formed fromshale crude oils with high naphthene to aromatics weight ratios/volumeratios. FIG. 3 also shows modeled values for an atmospheric residfraction formed from a representative light sweet crude. Additionally,FIG. 3 shows typical properties for a conventional very low sulfur fueloil (VLSFO), as well as some of the specifications for an RME 180 VLSFOfuel oil according to ISO 8217. The modeled atmospheric resid fractionshave an initial boiling point of 371° C., a T10 distillation pointbetween 390° C. and 405° C., and a T90 distillation point between 575°C. and 620° C.

As shown in FIG. 3, all of the modeled high naphthene to aromaticsratio, low sulfur atmospheric resid fractions derived from shale crudeoil sources have a lower sulfur content than the conventionalatmospheric resid fraction. The sulfur content for the shale atmosphericresid fractions is less than 0.25 wt %, and is less than 0.07 wt % forfour of the five fractions, or less than 0.05 wt %, such as down to0.005 wt %. Additionally, because the modeled atmospheric residfractions have not been hydroprocessed, the weight ratio of aliphaticsulfur to total sulfur ranges from 0.35 to 0.76. Thus, the modeledatmospheric resid fractions have a weight ratio of aliphatic sulfur tototal sulfur of greater than 0.2, or greater than 0.3. This is incontrast to a hydroprocessed fraction, which would be expected to have aweight ratio of aliphatic sulfur to total sulfur of 0.1 or less.

The modeled high naphthene to aromatics ratio, low sulfur atmosphericresid fractions derived from shale crude oil sources also have a lowernitrogen content than the conventional atmospheric resid fraction. Thenitrogen content for the shale atmospheric resid fractions is less than2000 wppm, and is less than 800 wppm for four of the five fractions, orless than 600 wppm, such as down to 25 wppm or possibly still lower.Additionally, because the modeled atmospheric resid fractions have notbeen hydroprocessed, the weight ratio of basic nitrogen to totalnitrogen ranges from 0.30 to 0.37. Thus, the modeled atmospheric residfractions have a weight ratio of basic nitrogen to total nitrogen ofgreater than 0.2, or greater than 0.3. This is in contrast to ahydroprocessed fraction, which would be expected to have a weight ratioof basic nitrogen to total nitrogen less than 0.2, or less than 0.1.

The modeled high naphthene to aromatics ratio, low sulfur atmosphericresid fractions also have a lower kinematic viscosity at 50° C., and alower density at 15° C. than the conventional atmospheric residfraction. The density for the shale atmospheric resid fractions is lessthan 915 kg/m³ for the shale atmospheric resid fractions, and is lessthan 900 kg/m³ for four of the five fractions, or less than 890 kg/m³,such as down to 855 kg/m³. The kinematic viscosity at 50° C. is lessthan 180 cSt for the shale atmospheric resid fractions or less than 160cSt. For four of the five fractions, the kinematic viscosity at 50° C.is less than 130 cSt, or less than 110 cSt, such as down to 30 cSt.Additionally, all of the shale atmospheric resid fractions have a volumeratio of naphthenes to aromatics of greater than 0.8. Four of the fivefractions have a volume ratio of naphthenes to aromatics of 1.5 or more,or 2.0 or more, or 2.5 or more, such as up to 6.0 or possibly stillhigher. This corresponds to all of the shale atmospheric resid fractionshaving weight ratio of naphthenes to aromatics of greater than 0.75.Four of the five fractions have a weight ratio of naphthenes toaromatics of 1.5 or more, or 1.8 or more, or 2.0 or more, or 2.5 ormore, such as up to 6.0 or possibly still higher.

It is noted that the kinematic viscosity at 50° C. of the atmosphericresid from the conventional light sweet crude oil is greater than 180cSt. As a result, the conventional atmospheric resid does not meet thespecifications for an RME 180 fuel oil without some type ofmodification, such as blending with a distillate flux. Additionally, itis noted that the sulfur content of the atmospheric resid from theconventional light sweet crude oil is greater than 0.5 wt %. This meansthat some type of hydroprocessing or other sulfur treatment (or possiblyblending with a sufficient amount of low sulfur distillate) would beneeded for the atmospheric resid from the light sweet crude to be usedas a fuel oil (such as RMA 10).

Since blending and hydroprocessing would be needed anyway, fuel oils arenot conventionally made from atmospheric resid fractions. Instead, afurther distillation is usually performed to form a vacuum residfraction. This potentially allows additional value to be captured forthe 370° C.—565° C. portion of the atmospheric resid by allowing thislower boiling fraction to be incorporated into higher value products. Avacuum resid fraction, however, typically has a kinematic viscosity at50° C. that is substantially higher than the specification for use as afuel oil. In order to meet fuel oil specifications, a distillate istypically blended with the vacuum resid fraction to correct thekinematic viscosity to a desired level. The addition of distillatetypically reduces the flash point of the resulting blend to just abovethe minimum flash point for a fuel oil of roughly 60° C. By contrast,the shale oil atmospheric resid fractions shown in FIG. 3 have asufficiently low kinematic viscosity to used without addition of adistillate flux. As a result, a fuel oil formed based on a shale oilatmospheric resid fraction can have a flash point of 100° C. or more, or120° C. or more, or 150° C. or more, or 200° C. or more, such as up to250° C. or possibly still higher.

The shale oil atmospheric resid fractions in FIG. 3 have still otherpotentially beneficial features. These features can include a naphthenescontent of 30 vol % to 60 vol %, or 35 vol % to 60 vol %, or 40 vol % to60 vol %, or 45 vol % to 60 vol %; or expressed as wt %, a naphthenescontent of 30 wt % to 55 wt %, or 35 wt % to 55 wt %, or 40 wt % to 55wt %, or 45 wt % to 55 wt %. Another feature can be an aromatics contentof 45 wt %/45 vol % or less, or 35 wt %/35 vol % or less, or 30 wt %/30vol % or less, or 25 wt %/25 vol % or less, such as down to 10 wt %/10vol % or possibly lower. Yet another feature can be an unexpectedly lowmicro carbon residue for a resid fraction, such as a micro carbonresidue of 2.5 wt % or less, or 1.0 wt % or less, such as down to 0.05wt % or possibly still lower. Still other features can include ahydrogen content of 11.0 wt % or more; a nitrogen content of 2000 wppmor less, or 1000 wppm or less; a BMCI of 20 to 40, or 20 to 35; ann-heptane insolubles content of 0.01 wt % to 0.2 wt %, or 0.01 wt % to0.1 wt %; and a CCAI of 790 or less, or 770 or less, such as down to 740or possibly still lower.

For a fuel oil made from a shale oil atmospheric resid fraction as shownin FIG. 3, still other characteristics of the fuel oil can be related tocompositional differences that can be found in fractions that are notexposed to hydrotreating conditions. As noted above, aliphatic sulfur istypically easily removed from a petroleum fraction, while other types ofsulfur are removed more slowly. In some aspects, since hydrotreating isnot necessary to reduce the sulfur level, a fuel oil made from anatmospheric resid fraction with a high naphthene to aromatics ratio canhave an elevated ratio of aliphatic sulfur to total sulfur in the fueloil. Similarly, the amount of basic nitrogen (more easily removed underhydroprocessing conditions) can be high relative to the amount of totalnitrogen. Additionally, by avoiding the need for hydroprocessing, theamount of sodium and/or calcium in the fuel oil can be higher than aconventional low sulfur or very low sulfur fuel oil.

FIG. 4 shows modeled compositional values and properties for analternative type of resid fraction that includes both distillate andatmospheric resid. The modeled fractions in FIG. 4 could be formed, forexample, by distilling off the naphtha (and lighter) portions of a shalecrude oil. This can allow for still lower carbon intensity whenproducing a fuel oil, such as an RMA 10 very low sulfur fuel oilaccording to Table 1 of ISO 8217. FIG. 4 also shows modeled values for acorresponding fraction formed from the representative light sweet crude.Additionally, FIG. 4 shows typical properties for a conventional VLSFO,as well as some of the specifications for an RMA 10 VLSFO fuel oilaccording to ISO 8217. The modeled fractions in FIG. 4 have an initialboiling point of roughly 180° C., a T10 distillation point between 189°C. to 195° C., and a T90 distillation point between 480° C. and 550° C.

As shown in FIG. 4, all of the high naphthene to aromatics ratio, lowsulfur fuel oils derived from shale crude oil sources have a lowersulfur content than the conventional distillate plus atmospheric residfraction. The sulfur content for the shale alternative atmospheric residfractions is less than 0.15 wt %, and is less than 0.05 wt % for four ofthe five fractions, such as down to 0.002 wt %. Additionally, becausethe modeled atmospheric resid fractions have not been hydroprocessed,the weight ratio of aliphatic sulfur to total sulfur ranges from 0.33 to0.76. Thus, the modeled atmospheric resid fractions have a weight ratioof aliphatic sulfur to total sulfur of greater than 0.2, or greater than0.3. This is in contrast to a hydroprocessed fraction, which would beexpected to have a weight ratio of aliphatic sulfur to total sulfur of0.1 or less.

As shown in FIG. 4, all of the high naphthene to aromatics ratio, lowsulfur fuel oils derived from shale crude oil sources have a lowernitrogen content than the conventional distillate plus atmospheric residfraction. The nitrogen content for the shale alternative atmosphericresid fractions is less than 850 wppm, and is less than 250 wppm forfour of the five fractions, such as down to 10 wppm. Additionally,because the modeled alternative atmospheric resid fractions have notbeen hydroprocessed, the weight ratio of basic nitrogen to totalnitrogen ranges from 0.29 to 0.36. Thus, the modeled alternativeatmospheric resid fractions have a weight ratio of basic nitrogen tototal nitrogen of greater than 0.2, and greater than 0.3 for four of thefive fractions. This is in contrast to a hydroprocessed fraction, whichwould be expected to have a weight ratio of basic nitrogen to totalnitrogen less than 0.2, or less than 0.1.

As shown in FIG. 4, all of the high naphthene to aromatics ratio, lowsulfur fuel oils derived from shale crude oil sources also have a lowerkinematic viscosity at 50° C. and a lower density at 15° C. than theconventional atmospheric resid fraction. The sulfur content for theshale atmospheric resid fractions is less than 0.15 wt %, and is lessthan 0.05 wt % for four of the five fractions, such as down to 0.002 wt%. The density for the shale atmospheric resid fractions is less than860 kg/m³ for the shale atmospheric resid fractions, and is less than850 kg/m³ for four of the five fractions, or less than 845 kg/m³, suchas down to 810 kg/m³. The kinematic viscosity at 50° C. is less than 6.2cSt for the shale atmospheric resid fractions, and is less than 5.5 cStfor four of the five fractions, or less than 5.0 cSt, such as down to3.2 cSt.

Additionally, all of the shale distillate plus atmospheric residfractions have a weight ratio and volume ratio of naphthenes toaromatics of greater than 1.5, and four of the five fractions have aweight ratio and volume ratio of naphthenes to aromatics of greater than2.0, or greater than 3.0, such as up to 6.0 or possibly still higher.Relative to the atmospheric resids shown in FIG. 3, the alternativeresid fractions in FIG. 4 have higher paraffin contents in exchange forlower aromatic contents.

The shale oil resid fractions in FIG. 4 have still other potentiallybeneficial features. These features can include a naphthenes content of40 vol % to 55 vol %, or 43 vol % to 55 vol % (or 38 wt % to 55 wt %, or40 wt % to 55 wt %). Another feature can be an aromatics content of 28wt %/28 vol % or less, or 20 wt %/20 vol % or less, or 15 wt %/15 vol %or less, such as down to 5.0 wt %/5 vol % or possibly lower. Yet anotherfeature can be an unexpectedly low micro carbon residue for a residfraction, such as a micro carbon residue of 1.0 wt % or less, or 0.5 wt% or less, such as down to 0.02 wt % or possibly still lower. Stillother features can include a hydrogen content of 13.5 wt % or more (or13.9 wt % or more); a nitrogen content of 850 wppm or less, or 250 wppmor less; a BMCI of 20 to 35, or 20 to 30; an n-heptane insolublescontent of 0.05 wt % or less, or 0.03 wt % or less, such as down to 0.01wt %; and a CCAI of 790 or less, or 780 or less, such as down to 740 orpossibly still lower.

Fuel Oil and Marine Gas Oil Blends Including Shale Oil AtmosphericResids

In various examples below, a variety of refinery fractions, renewablefractions and finished fuels are used as representative blendingcomponents for the formation of fuel blends. The fuel blends are formedby blending one or more low sulfur, high naphthene to aromatic ratioshale oil fractions with one or more of the refinery fractions,renewable fractions, or finished fuels.

As described above, atmospheric resid fractions derived from low sulfur,high naphthene to aromatic shale oils can be used as fuel oils afterreduced or minimized amounts of processing. This can have acorresponding effect of reducing or minimizing the carbon intensity ofthe resulting fuel due to refinery processing. In addition to using thelow carbon intensity atmospheric resids as fuel oils, the atmosphericresids can also be blended with other low carbon intensity fractions toform still lower carbon intensity fuels.

As an example, distillates derived from biological sources can have asubstantially lower carbon intensity, due in part to the consumption ofcarbon during the formation of the biomass. By blending a low carbonintensity atmospheric resid with a biodiesel (or other renewabledistillate fraction) can result in a fuel or fuel blending componentwith a reduced or minimized carbon intensity. Blending a shale oilatmospheric resid fraction with biodiesel can also provide unexpectedsynergistic advantages. For example, shale oil atmospheric resids cantend to have a relatively high pour point, so the biodiesel can also actas a pour point corrector. Biodiesel can also tend to have high solvencyfor asphaltenes, so blending biodiesel with a shale oil atmosphericresid can improve the ability to combine the resulting blended productwith other resid fractions.

Another potential blending route for low carbon intensity atmosphericresids can be to blend an atmospheric resid with a low sulfur distillateblendstock (such as ultra low sulfur diesel) to form marine gas oilsand/or very low sulfur fuel oils. It has been discovered thatsubstantially larger amounts of low carbon intensity atmospheric residscan be blended with conventional distillate fuels while still forming amarine gas oil that satisfies the requirements of a DMB and/or DFBmarine gas oil according to ISO 8217. In particular, due to theunexpectedly low micro carbon residue of the atmospheric resids, blendsof up to 50 vol % atmospheric resid with 50 vol % distillate can beformed while still meeting the requirements of a DMB or DFB marine gasoil. Blends containing up to 55 vol % atmospheric resid with distillatecan also be formed while satisfying the specifications for a fuel oil,such as a RMA 10 fuel oil according to ISO 8217. Thus, blends including1.0 vol % to 50 vol % of atmospheric resid, or 1.0 vol % to 55 vol %atmospheric resid, can be used to form marine gas oils.

The first two columns of Table 1 show two types of biodiesels that wereused as blend components for modeling of the formation of fuel oils andmarine gas oils. The third column shows a commercial ultra low sulfurdiesel that was used for modeling of blending with shale oil atmosphericresid to form fuel oils and marine gas oils.

TABLE 1 Atmospheric Resid Blend Components (Modeled) Biodiesel 1Biodiesel 2 ULSD Density at 881.1 879.6 830.6 15° C. (kg/m3) KV50 (cSt)3.5 3.734 2.362 Sulfur (ppm ~5 ~5 0.00039 m/m) CCAI 828 824 BMCI 55 8026.8 TE 0 0 MCR (wt %) 0 0 0 Cloud Point −1 >1 Pour Point (° C.) <−5 6

Table 2 shows modeling results for blending atmospheric resids from FIG.3 with varying amounts of biodiesel.

TABLE 2 Low Carbon Intensity Fuel Oil Blends (Modeled) 90% 95% 40% 40%FO1 + FO3 + FO3 + FO3 + ISO8217 10% 5% 60% 60% RMD80 Biodiesel BiodieselBiodiesel Biodiesel Spec 1 1 1 2 Density at <990 0.8684 0.9071 892.1891.2 15° C. (kg/m3) KV50 (cSt) <80 35.3 105 10.1 10.6 Sulfur <0.50 1260.207 0.089 0.089 (wt %) CCAI <860 760 783 809 807 BMCI — 28 41 49 64 TE— 0 0 0 0 N-Heptane — 0.04 0.07 0.03 0.03 Insolubles (wt %) MCR <14 0.052.33 1.00 1.00 (wt %) Pour Point <30 ~30 ~29 ~9 ~16 (° C.)

As shown in Table 2, low carbon intensity fuel oils that satisfy thespecifications for an RMD80 fuel oil can be formed with blends rangingfrom 5 vol % to 60 vol % in biodiesel, with the balance (40 vol % to 95vol %) corresponding to low carbon intensity atmospheric resid. Becauseof the low, sulfur content, density, and kinematic viscosity of the lowcarbon intensity atmospheric resid fractions, even addition of 5 vol %of biodiesel can result in a blend with satisfactory properties.Additionally, addition of 5 vol % or 10 vol % of biodiesel can besufficient to form a blended fuel oil product with a pour point of 30 orless. More generally, low carbon fuels can be formed that include 5 wt %to 95 wt % of a shale oil atmospheric resid having a high naphthene toaromatic ratio and a low sulfur content. Also more generally, anyconvenient type of renewable distillate can be used, such as biodiesel,hydrotreated vegetable oil, or another convenient distillate boilingrange fraction derived from a renewable source.

Modeling was also used to combine the atmospheric resids of FIG. 3 witha commercial ultra low sulfur diesel (ULSD) fraction to form potentialmarine gas oils or fuel oils. Based on the modeling, in contrast toconventional blends of distillates with resid fractions, it wasdiscovered that compatibility and/or sediment formation was not aprimary factor in determining whether a blend could form a fuel thatsatisfied one or more fuel specifications. Instead, it was discoveredthat the micro carbon residue content was the controlling factor. Due tothe low micro carbon residue content of the low carbon intensityatmospheric resid fractions, it was discovered that substantial amountsof atmospheric resid could be added.

FIG. 15 shows modeling results for blending of fuel oils (i.e., modeledatmospheric resids) from FIG. 3 with the ULSD fraction. As shown in FIG.15, for fuel oil 4, between 30 vol % and 50 vol % of atmospheric residcould be included in the blend while still satisfying the requirementsfor a DMB or DFB gas oil. Further addition of fuel oil 4 resulted in amicro carbon residue value outside of the gas oil specification.However, addition of 50 vol % of fuel oil 4 still provided asufficiently low micro carbon residue value to satisfy thespecifications for a RMA 10 fuel oil. For fuel oil 1, between 50 vol %and 55 vol % of the atmospheric resid could be included in the blendwhile satisfying the specification for a DMB or DFB gas oil, while 55vol % of atmospheric resid could be included while satisfying thespecifications for a RMA 10 fuel oil. For fuel oil 3, between 10 vol %and 20 vol % of the atmospheric resid could be included in the blendwhile satisfying the specification for a DMB or DFB gas oil, while 45vol % of atmospheric resid could be included while satisfying thespecifications for a RMA 10 fuel oil.

In contrast to the above results, when blending commercial ULSD withvarious types of commercial low sulfur fuel oils, addition of even 5 vol% of commercial fuel oil to the blend would result in a micro carbonresidue content in excess of the specification for a DMB or DFB gas oil.Additionally, between only 10 vol % and 20 vol % of commercial fuel oilcould be added to the commercial ULSD while still meeting the microcarbon residue specification for a RMA 10 fuel oil.

Table 3 shows properties for conventional ultra low sulfur diesels andconventional resid fractions. Table 3 shows properties for theconventional diesel and resid fractions. It is noted that comparativedistillate blendstocks A and B correspond to ultra low sulfur dieselfuels, while the comparative resid blendstocks A and B both correspondto commercially available fuel oils.

TABLE 3 Comparative Distillate and Resid Blendstocks Comp. Comp. Comp.Comp. Distillate Resid Distillate Resid Test Blend- Blend- Blend- Blend-Property Method stock A stock A stock B stock B Density at ASTM 0.82860.9643 0.8502 976.6 15° C., D4052 kg/L Sulfur, ASTM 0.00054 2.59 0.00031.3 wt % D4294 or ASTM D5453 KV50, cSt ASTM — 351.8 2.435 410.5 D445Sediment, ISO 0 0.01 0 — wt % 10307-2 Asphaltene IP 143 0 5.3 0 2.6Content, wt % Micro ASTM 0 15.5 0 12.6 Carbon D4530 Residue, % mass

Table 4 shows blend compositions produced by blending various amounts ofComparative Distillate Blendstock A and Comparative Resid Blendstock A.As shown in Table 4, addition of 2 vol % of the resid blendstock resultsin a micro carbon residue content that is too high to satisfy the DMBspecification. Addition of 5 vol % of resid blendstock results in amicro carbon residue content that is too high to satisfy the RMA10specification.

TABLE 4 Blends Based on Distillate Blendstock A and Resid Blendstock ABlend #  1  2  3  4  5 ISO ISO Distillate Blendstock 2, vol % 99 98 9590 80 8217 8217 Resid Blendstock 2, vol %  1  2  5 10 20 DMB/ RMAProperty Method Result Result Result Result Result DFB 10 Sediment, %10307-2* 0.01 0.01 0.01 0.01 0.01 Max Max mass 0.1 0.1 MCR, % mass ASTMD4530 0.21^(†) 0.41^(†) 0.91^(†) 1.81^(†) 3.51^(†) 0.30 2.50

As another comparative example, Comparative Distillate Blendstock B andComparative Resid Blendstock B were blended in a volume ratio of 70 vol% distillate to 30 vol % to resid. This resulted in a blendedcomposition that contained 3.6 wt % of micro carbon residue, which iswell above the specification for either a DMB or an RMA10 fuel. Thisblend also resulted in a sediment mass of 0.2 wt %, which is greaterthan the fuel specification value.

Characterization of Shale Oil Fractions—Distillate Fractions andCorresponding Marine Gas Oils

In some aspects, a distillate fraction of a shale oil as describedherein can be used as a marine gas oil or as a blending component for amarine gas oil. The combination of low sulfur, high naphthene toaromatics ratio, low density, and low kinematic viscosity can allow adistillate fraction to be used as a marine gas oil with reduced orminimized processing, such as possibly using the fraction as a marinegas oil after distillation without further processing.

FIG. 5 shows measured data for distillate boiling range fractionsderived from seven different shale oil and/or shale oil blends. Thedistillate cuts shown in FIG. 5 are narrow distillate cuts, with a T10distillation point of roughly 290° C.-300° C. and a T90 distillationpoint of roughly 350° C. to 360° C. This corresponds roughly to a heavydiesel fraction after removing a jet fuel or kerosene portion. As shownin FIG. 5, these distillate fractions derived from shale crude oilsand/or blends of shale crude oils had a relatively low specific gravityat 15° C. of 830 kg/m³ to 860 kg/m³, which indicates the presence of anunexpectedly high ratio of naphthenes to aromatics in the distillatefractions. The distillate fractions also had other unexpectedcombinations of properties, including an unexpectedly high derivedcetane number of 60-72, or 62-72; a sulfur content of less than 0.1 wt%, or less than 0.05 wt %, or less than 0.025 wt %; and a nitrogencontent of less than 200 wppm, or less than 100 wppm.

FIG. 6 shows modeled data for distillate boiling range fractions(including a portion of kerosene boiling range compounds) derived fromthe first five shale crude oils shown in FIG. 5. The modeled distillatefractions shown in FIG. 6 have an initial boiling point of 148° C. and afinal boiling point of 432° C. This results in a modeled T10distillation point of 185° C. to 195° C. and a T90 distillation point of365° C. to 385° C. More generally, the T10 distillation point can bebetween 150° C. and 230° C. As shown in the modeled compositional valuesand properties in FIG. 6, the distillate fractions have an unexpectedlyhigh weight ratio and/or volume ratio of naphthenes (cycloparaffins) toaromatics of 2.5 or more, or 3.0 or more, such as up to 8.0 or possiblystill higher, while also including 5.0 wt % to 18 wt % aromatics, or 5.0wt % to 15 wt %, or 5.0 wt % to 12 wt % (or 5.0 vol % to 18 vol %, or5.0 vol % to 15 vol %, or 5.0 vol % to 12 vol %). The distillatefractions further have an unexpected combination of a low density at 15°C. of 810 kg/m³ to 835 kg/m³ (or 810 kg/m³ to 830 kg/m³); an energycontent of 42.9 MJ/kg or greater; a low kinematic viscosity at 40° C. of2.5 cSt to 2.8 cSt; a low sulfur content of 0.004 wt % to 0.01 wt %, or0.005 wt % to 0.009 wt %; a low nitrogen content of 150 wppm or less, or100 wppm or less, or 50 wppm or less, such as down to 1.0 wppm; and anacid number of less than 0.1 mg KOH/kg, or less than 0.08 mg KOH/kg.More generally, the kinematic viscosity at 40° C. can be 2.0 cSt to 4.0cSt, or 2.5 cSt to 3.2 cSt. The distillate boiling range fractions canalso have a cetane index of 45 or more, or 49 or more, such as up to 65or possibly still higher. Based on the sulfur content, density, andkinematic viscosity, the distillate boiling range fractions in FIG. 6can be used as a marine gas oil with a reduced or minimized amount ofadditional processing. For example, the distillate boiling rangefractions in FIG. 6 can be used as a DMA marine gas oil afterdistillation to form the distillate boiling range fraction.

FIG. 7 shows comparative data corresponding to modeled distillateboiling range fractions with comparable boiling ranges relative to FIG.6 from three representative conventional crudes. Comparative distillatefraction A corresponds to a fraction derived from a light sweet crude.Comparative distillate fractions B and C correspond to fractions derivedfrom heavy sour crudes. FIG. 7 further shows some specifications forforming a DMA marine gas oil according to ISO 8217.

As shown in FIG. 7, the comparative distillate fractions have weightratios/volume ratios of naphthenes to aromatics that are less than 2.5,as well as sulfur contents of 0.3 wt % or more. Based on the sulfurcontent, any of the comparative fractions shown in FIG. 7 would requireat least hydrotreating prior to use as a marine gas oil. Thus, thecarbon intensity for a marine gas oil formed from one of thesecomparative fractions would be higher. The energy content of thecomparative fractions is also lower, at 42.8 MJ/kg or less.Additionally, the comparative fractions have cetane index values below50. The comparative fractions also have substantially higher densitiesand kinematic viscosities.

FIG. 8 shows modeled compositional features and properties foralternative distillate fractions formed from five of the seven shalecrude oils. The alternative distillate fractions have an initial boilingpoint of 148° C. and a final boiling point of 464° C., so that aslightly greater portion of vacuum gas oil boiling range compounds isincluded in the fractions. This results in a modeled T10 distillationpoint of 185° C. to 195° C. and a T90 distillation point of 380° C. to405° C. As shown in the modeled compositional values and properties inFIG. 8, the distillate fractions have an unexpectedly high weight ratioand/or volume ratio of naphthenes (cycloparaffins) to aromatics of 2.5or more, or 3.0 or more, such as up to 8.0 or possibly still higher,while also including 5.0 wt % to 18 wt % aromatics, or 5.0 wt % to 15 wt%, or 5.0 wt % to 12 wt % (or 5.0 vol % to 18 vol % aromatics, or 5.0vol % to 15 vol %, or 5.0 vol % to 12 vol %). The distillate fractionsfurther have an unexpected combination of a low density at 15° C. of 810kg/m³ to 840 kg/m³ (or 810 kg/m³ to 830 kg/m³); an energy content of42.9 MJ/kg or greater; a low kinematic viscosity at 40° C. of 2.8 cSt to3.2 cSt; a low sulfur content of 0.04 wt % to 0.10 wt %, or 0.05 wt % to0.09 wt %; a low nitrogen content of 200 wppm or less, or 100 wppm orless, or 50 wppm or less, such as down to 5.0 wppm; and an acid numberof less than 0.1 mg KOH/kg, or less than 0.08 mg KOH/kg.

FIG. 9 shows comparative data corresponding to modeled distillateboiling range fractions with comparable boiling ranges relative to FIG.8 from three representative conventional crudes. Comparative distillatefraction A corresponds to a fraction derived from a light sweet crude.Comparative distillate fractions B and C correspond to fractions derivedfrom heavy sour crudes. FIG. 9 further shows some specifications forforming a DMA marine gas oil according to ISO 8217.

As shown in FIG. 9, the comparative distillate fractions have weightratios/volume ratios of naphthenes to aromatics that are less than 2.5,as well as sulfur contents of 0.3 wt % or more. Based on the sulfurcontent, any of the comparative fractions shown in FIG. 9 would requireat least hydrotreating prior to use as a marine gas oil. Thus, thecarbon intensity for a marine gas oil formed from one of thesecomparative fractions would be higher. Additionally, the comparativefractions have cetane index values below 50. The comparative fractionsalso have higher densities and kinematic viscosities.

Characterization of Shale Oil Fractions—Vacuum Gas Oils andCorresponding Fuel Oils

In some aspects, a vacuum gas oil fraction of a shale oil as describedherein or a fraction can be used as a marine fuel oil or as a blendingcomponent for a marine fuel oil. The combination of low sulfur, highnaphthene to aromatics ratio, low density, and low kinematic viscositycan allow a vacuum gas oil to be used as a marine fuel oil with reducedor minimized processing, such as possibly using the fraction as a fueloil after distillation without further processing.

FIG. 10 and FIG. 11 show measured compositional features and propertiesfor vacuum gas oil fractions formed from seven shale crude oils and/orshale crude oil blends. The vacuum gas oil cuts shown in FIG. 10 andFIG. 11 had a T10 distillation point of roughly 365° C.-380° C. and aT90 distillation point of roughly 500° C. to 525° C. As shown in FIG. 10and FIG. 11, these vacuum gas oil fractions derived from shale crudeoils and/or blends of shale crude oils had a relatively low density at15° C. of 850 kg/m³ to 890 kg/m³, which indicates the presence of anunexpectedly high ratio of naphthenes to aromatics in the vacuum gas oilfractions. The unexpectedly high ratio of napthenes to aromatics isfurther indicated by the high saturates content of the fractions of 75wt % or more. The vacuum gas oil fractions also had other unexpectedcombinations of properties, including an unexpectedly low kinematicviscosity; a sulfur content of less than 0.1 wt %, or less than 0.05 wt%, or less than 0.025 wt %; and a nitrogen content of less than 500wppm, or less than 350 wppm.

FIG. 12 shows modeled data for the five vacuum gas oils shown in FIG.10. The modeled vacuum gas oil fractions shown in FIG. 12 have aninitial boiling point of 371° C. and a final boiling point of 538° C.This results in a modeled T10 distillation point of 385° C. to 395° C.and a T90 distillation point of 480° C. to 490° C. As shown in themodeled compositional values and properties in FIG. 12, the vacuum gasoil fractions have an unexpectedly high weight ratio/volume ratio ofnaphthenes (cycloparaffins) to aromatics of 1.0 or more, or 1.5 or more,or 2.0 or more, such as up to 6.0 or possibly still higher, while alsoincluding 8.0 wt % to 33 wt % aromatics, or 8.0 wt % to 22 wt %, or 10wt % to 33 wt %, or 10 wt % to 22 wt % (or 8.0 vol % to 33 vol %, or 8.0vol % to 22 vol %, or 10 vol % to 33 vol %, or 10 vol % to 22 vol %).Four of the five vacuum gas oil fractions have a naphthenes content of40 wt %/40 vol % or more. The vacuum gas oil fractions further have anunexpected combination of a low density at 15° C. of 860 kg/m³ to 892kg/m³ (or 860 kg/m³ to 882 kg/m³); an energy content of 42.4 MJ/kg orgreater; a low kinematic viscosity at 50° C. of 20 cSt to 30 cSt; a lowsulfur content of 0.03 wt % to 0.20 wt %; a low nitrogen content of 1000wppm or less, or 850 wppm or less, or 350 wppm or less, such as down to30 wppm; a CCAI value of 760 to 785; a molar ratio of hydrogen to carbonof greater than 1.8; and an acid number of less than 0.15 mg KOH/kg, orless than 0.12 mg KOH/kg. Based on the sulfur content, density, andkinematic viscosity, the vacuum gas oil boiling range fractions in FIG.12 can be used as a fuel oil with a reduced or minimized amount ofadditional processing. For example, the vacuum gas oil boiling rangefractions in FIG. 12 can be used as a RMD 80 very low sulfur fuel oilaccording to ISO 8217 after distillation to form the distillate boilingrange fraction.

FIG. 13 shows comparative data corresponding to modeled comparablevacuum gas oil boiling range fractions from three representativeconventional crudes. Comparative vacuum gas oil fraction A correspondsto a fraction derived from a light sweet crude. Comparative vacuum gasoil fractions B and C correspond to fractions derived from heavy sourcrudes. FIG. 13 also shows values for a hydrotreated vacuum gas oilfraction, as described in U.S. Pat. No. 8,999,011. FIG. 13 further showssome specifications for forming a RMD80 very low sulfur fuel oilaccording to ISO 8217.

As shown in FIG. 13, the comparative vacuum gas oil fractions haveweight ratios/volume ratios of naphthenes to aromatics that are lessthan 1.5, or less than 1.0, as well as sulfur contents of 0.6 wt % ormore. Based on the sulfur content, any of the comparative vacuum gas oilfractions shown in FIG. 13 would require at least hydrotreating prior touse as a very low sulfur fuel oil. Thus, the carbon intensity for a fueloil formed from one of these comparative fractions would be higher. Theenergy content of the comparative fractions is also lower, at 42.2 MJ/kgor less. Additionally, the comparative fractions have a molar ratio ofhydrogen to carbon of less than 1.8. The comparative fractions also havehigher densities and kinematic viscosities.

Fuel Oil Blends Including Shale Vacuum Gas Oils

In the examples below, a variety of refinery fractions, renewablefractions and finished fuels are used as representative blendingcomponents for the formation of fuel blends. The fuel blends are formedby blending one or more low sulfur, high naphthene to aromatic ratioshale oil fractions with one or more of the refinery fractions,renewable fractions, or finished fuels.

As described above, vacuum gas oil fractions derived from low sulfur,high naphthene to aromatic shale oils can be used as fuel oils afterreduced or minimized amounts of processing. This can have acorresponding effect of reducing or minimizing the carbon intensity ofthe resulting fuel due to refinery processing. In addition to using thelow carbon intensity vacuum gas oils as fuel oils, the vacuum gas oilscan also be blended with other low carbon intensity fractions to formstill lower carbon intensity fuels.

As an example, distillates derived from biological sources can have asubstantially lower carbon intensity, due in part to the consumption ofcarbon during the formation of the biomass. Blending a shale oil vacuumgas oil fraction with biodiesel and/or another renewable distillate canalso provide unexpected synergistic advantages. For example, shale oilvacuum gas oils can also tend to have a relatively high pour point, sothe biodiesel can also act as a pour point corrector. Biodiesel can alsotend to have high solvency for asphaltenes, so blending biodiesel with ashale oil atmospheric resid can improve the ability to combine theresulting blended product with other resid fractions.

Another potential blending route for low carbon intensity vacuum gasoils can be to blend a vacuum gas oil with a conventional resid fractionto form low sulfur or very low sulfur fuel oils. The low density ofthese low carbon intensity vacuum gas oils means that they could be usedto correct density in a blend, thereby expanding the use of high densitycomponent such as LCO, HCO, FCC bottoms, and visbreaker tars for makingmarine fuel oils. These low carbon intensity vacuum gas oils could alsobe used to correct sulfur, viscosity and CCAI in a blend, making it aversatile blend component. Additionally, the low carbon intensity vacuumgas oils have a viscosity at 50° C. about 10 times higher than a middledistillate. Thus, a low carbon intensity vacuum gas oil could be blendedat a high level into a fuel oil and yet maintain a viscosity at 50°C.>10 cSt, which is the minimum viscosity preferred for optimaloperation of the fuel injection system in a marine engine.

The first two columns of Table 5 show two types of biodiesels that wereused as blend components for forming fuel oils and marine gas oils. Thefinal two columns show two types of hydrotreated vegetable oils thatwere used as blend components for forming fuel oils.

TABLE 5 Vacuum Gas Oil Blend Components (Model) Biodiesel 1 Biodiesel 2HVO1 HVO2 Density at 881.1 879.6 795.5 777.7 15° C. (kg/m3) KV50 (cSt)3.5 3.734 3.076 2.299 Sulfur (ppm ~5 ~5 ~5 ~5 m/m) CCAI 828 824 746 741BMCI 55 80 4 −2 TE 0 0 0 0 MCR (wt %) 0 0 0 0.4 Cloud Point −1 >1 10 −10Pour Point (° C.) <−5 6 10 −10

Table 6 shows modeling results for blending vacuum gas oils from FIG. 12with varying amounts of biodiesel or hydrotreated vegetable oil.

TABLE 6 Low Carbon Intensity Fuel Oil Blends Based on Vacuum Gas Oil 90%55% 90% 55% ISO8217 HD5 + HD3 + HD5 + HD3 + RMD80 10% 45% 10% 45% SpecBiodiesel 1 Biodiesel 2 HVO 2 HVO 1 Density at <990 878.7 885.4 868.30.8523 15° C. (kg/m3) Viscosity <80 19.8 9.9 18.2 8.7 at 50° C. (cSt)Sulfur <0.50 342 926 346 967 (wt %) CCAI <860 781 803 772 768 BMCI — 3255 27 21 TE — 0 0 0 0 N-Heptane — 0.00 0.00 0.00 0.00 Insolubles (wt %)MCR <14 0.07 0.10 0.07 0.11 (wt %) Pour Point <30 ~30 ~23 ~30 ~25 (° C.)

As shown in Table 6, low carbon intensity fuel oils that satisfy thespecifications for an RMD80 fuel oil can be formed with blends rangingfrom 10 vol % to 45 vol % in biodiesel, with the balance (55 vol % to 90vol %) corresponding to low carbon intensity vacuum gas oil. Because ofthe low, sulfur content, and density of the low carbon intensity vacuumgas oil fractions, addition of 10 vol % of biodiesel or hydrotreatedvegetable oil can result in a blend with satisfactory properties. Highercontents of biodiesel or hydrotreated vegetable oil, such as up to 45vol %, can also be used due to the higher kinematic viscosity of thevacuum gas oil relative to a middle distillate fraction. Additionally,inclusion of 10 vol % or more of biodiesel or hydrotreated vegetable oilcan be sufficient to form a blended fuel oil product with a pour pointof 30 or less.

Characterization of Shale Oil Fractions—Vacuum Resids and CorrespondingFuel Oil Blends

Vacuum resid fractions correspond to fractions with T10 distillationpoints of roughly 500° C. or more. The kinematic viscosity of vacuumresid fractions derived from shale crude oil is typically too high to beused directly as a fuel oil. However, the other properties of a shaleoil vacuum resids can allow the vacuum resids to serve as beneficialblending components.

For example, based on the low sulfur content, high energy content andlow CCAI, shale oil vacuum resids can be beneficial fuel oil blendcomponents to produce 0.1 wt % sulfur (ECA fuel oils) and 0.5 wt %sulfur fuel oils (VLSFO). The low density of the vacuum resids meansthat they can be used to correct density in a blend, thereby expandingthe use of high density component such as LCO, HCO, FCC bottoms andvisbreaker tars for making marine fuel oils.

FIG. 14 shows modeling of vacuum resid fractions for the five types ofshale crude oils or shale crude oil blends shown in FIG. 3. The modeledvacuum resid fractions in FIG. 14 have an initial boiling point of 538°C. and a final boiling point greater than 600° C. As shown in FIG. 14,the vacuum resid fractions have a low density of 880 kg/m³ to 950 kg/m³,or 880 kg/m³ to 920 kg/m³. The vacuum resid fractions also have a lowsulfur content of 0.35 wt % or less, or 0.1 wt % or less. The CCAI ofthe vacuum resids is also low, with values between 720 and 780, orbetween 720 and 750. Additionally, four of the five vacuum resids havean unexpectedly high weight ratio/volume ratio of naphthenes toaromatics of 1.0 or more, or 1.5 or more. For the four vacuum resids,this is due to having a naphthenes content of greater than 38 wt %/38vol %, or greater than 40 wt %/40 vol %, and an unexpectedly lowaromatics content of 20 wt % to 42 wt % (or 20 vol % to 42 vol %).

Modeled examples of blending these fuel oil components with light cycleoil (LCO), gas oil and biodiesel to make finished ECA fuel oil and verylow sulfur fuel oil (VLSFO) are given in Tables 7 and 8. In the LCOexamples in Table 7, the density, CCAI and sulfur are simultaneouslyreduced in the blends containing VR Fuel Oil 1 or 3 from FIG. 14, whichmeets the VLSFO spec. In the gas oil examples, an ECA fuel oil productis made from VR Fuel Oils 2 and 5 because gas oil corrects the high pourpoint and viscosity of the fuel oil components while maintaining asulfur content below 0.1 wt %.

TABLE 7 Vacuum Resid Blends 55% 35% 35% 75% LCO, LCO, Gas Oil, Gas Oil,45% 60% 65% 25% ISO8217 VRFO1, VRFO3, VRFO2, VRFO5, RMD80 VLSFO, VLSFO,ECA, ECA, high Spec high ratio low ratio low ratio ratio Density at <990901.8 936.9 8771 870.3 15° C. (kg/m3) KV50 (cSt) <80 28 202 112 11.6Sulfur <0.50 0.4808 0.4950 0.0403 0.0593 (wt %) CCAI <860 798 805 752784 BMCI — 42 54 25 31 TE — 6 4 0 0 N-Heptane — 0.15 0.16 0.15 0.02Insolubles (wt %) MCR <14 0.18 4.58 0.34 0.74 (wt %) Pour Point <30 2124 29 14 (° C.)

The biodiesel blends in Table 8 demonstrate that a wide range ofbiodiesel blend ratios is possible while having viscosity, pour pointand sulfur content meets the requirements of an ECA or VLSFO product.

TABLE 8 Vacuum Resid Blends with Renewable Distillates 25% 50% 30% 70%Biodiesel, Biodiesel, Biodiesel, Biodiesel, 75% 50% 70% 30% ISO8217VRFO5, VRFO1, VRFO3, VRFO3, RMD80 ECA, ECA, VLSFO, VLSFO, Spec low ratiohigh ratio low ratio low ratio Density at <990 907.0 880.9 926.9 0.899915° C. (kg/m3) KV50 (cSt) <80 366 33.0 298 13.8 Sulfur (wt %) <0.500.0592 0.0148 0.2269 0.1004 CCAI <860 768 774 790 810 BMCI — 46 50 59 71TE — 0 0 0 0 N-Heptane — 0.05 0.11 0.14 0.06 Insolubles (wt %) MCR (wt%) <14 2.14 0.11 4.93 2.18 Pour Point <30 29 27 28 15 (° C.)

Properties for the LCO, gas oil, and biodiesel used in Tables 7 and Bareprovided in Table 9.

TABLE 9 Blend Components for Vacuum Resid Blends LCO Gas Oil Biodiesel 2Density at 918.0 855.0 879.6 15° C. (kg/m3) KV50 (cSt) 4.2 4.27 3.734Sulfur (ppm 8260 526 ~5 m/m) CCAI 858 795 824 BMCI 61.3 30 80 TE 17.5 00 MCR (wt %) 0.2 <0.001 0 Cloud Point — ? >1 Pour Point (° C.) −6 6 6

ADDITIONAL COMPARATIVE EXAMPLES

The resid-containing, distillate, and vacuum gas oil compositions andblends described herein can be formed from selected types of crude oils,such as selected types of shale crude oils. Table 10 shows somecomparative fractions that roughly correspond to vacuum gas oil boilingrange fractions. The fractions shown in Table 10 were described in anarticle titled “Catalytic Solutions for Processing Shale Oils in theFCC” (www.digitalrefining.com, April 2014).

TABLE 10 Comparative VGO Fractions Eagle Ford VGO Bakken Condensatederived Crude Splitter from 85% 650° F. + Mid-Continent Bottoms EagleFord bottoms VGO API Gravity 36.6 30 23 24.7 Sulfur (wt %) 0.08 0.830.43 0.35 Aromatic ring 14.8 15.2 22.1 17.6 carbons Naphthene ring 19.49.8 17.3 20.3 carbons Paraffinic 65.8 75 60.6 62.1 carbons D2887 (° F.)T10 519 715 658 691 T50 735 862 844 848 T90 1006 1015 1135 1045

The Eagle Ford and Bakken fractions shown in Table 10 correspond toshale fractions, while the Mid-Continent VGO corresponds to aconventional fraction. The fractions in Table 10 roughly correspond tovacuum gas oil fractions, although the first column (splitter bottoms)includes some distillate. In Table 10, the aromatic carbons andnaphthene carbons are reported based on the percentage of carbons thatare present in ring structures, rather than providing a total weightpercent for naphthenes or aromatics. However, this should not have asignificant impact on the ratio of napthenes to aromatics.

As shown in Table 10, all of the comparative vacuum gas oil fractionshave naphthenic carbon to aromatic carbon ratios of less than 1.5. Thisis in contrast to the vacuum gas oil fractions shown in FIG. 12, wherefour of the five fractions have naphthenes to aromatics weight ratios ofgreater than 2.0. This further illustrates the unexpected nature of theatmospheric resid, vacuum resid, and vacuum gas oil compositionsdescribed herein.

ADDITIONAL EMBODIMENTS

Embodiment 1. A resid-containing fraction comprising a T90 distillationpoint of 550° C. or more, a kinematic viscosity at 50° C. of 40 cSt to150 cSt, a sulfur content of 0.2 wt % or less, a BMCI of 40 or less, anda weight ratio of aliphatic sulfur to total sulfur of 0.2 or more.

Embodiment 2. The resid-containing fraction of Embodiment 1, wherein theresid-containing fraction comprises a weight ratio of naphthenes toaromatics of 1.5 or more, or wherein the resid-containing fractioncomprises a flash point of 120° C. or more, or a combination thereof.

Embodiment 3. A fuel composition comprising 5 vol % to 60 vol % of adistillate fraction and 40 vol % to 95 vol % of the resid-containingfraction of Embodiment 1 or 2.

Embodiment 4. The fuel composition of Embodiment 3, wherein thedistillate fraction comprises a renewable distillate fraction, therenewable distillate fraction comprising one or more of biodiesel, fattyacid alkyl ester, and hydrotreated vegetable oil; or wherein therenewable distillate comprises a distillate made, processed or acombination thereof using a renewable energy source; or wherein therenewable distillate comprises a distillate formed from processing ofbiologically derived waste, or a combination thereof.

Embodiment 5. A fuel composition comprising: a) 50 vol % to 99 vol % ofa distillate fraction and 1.0 vol % to 50 vol % of a resid-containingfraction, a micro carbon residue content of 0.30 wt % or less, akinematic viscosity at 40° C. of 11 cSt or less, and a sulfur content of0.5 wt % or less; orb) 45 vol % to 99 vol % of the distillate fractionand 1.0 vol % to 55 vol % of the resid-containing fraction, a microcarbon residue content of 2.5 wt % or less, a kinematic viscosity at 50°C. of 10 cSt or less, and a sulfur content of 0.5 wt % or less, whereinthe resid-containing fraction comprises a T90 distillation point of 550°C. or more, a kinematic viscosity at 50° C. of 40 cSt to 150 cSt, asulfur content of 0.2 wt % or less, a BMCI of 40 or less, and a weightratio of aliphatic sulfur to total sulfur of 0.2 or more.

Embodiment 6. A resid-containing fraction comprising a T10 distillationpoint of 150° C. to 200° C., a T90 distillation point of 550° C. ormore, a kinematic viscosity at 50° C. of 3.0 cSt to 7.0 cSt, a sulfurcontent of 0.2 wt % or less, a density at 15° C. of 860 kg/m³ or less, aBMCI of 35 or less, a weight ratio of naphthenes to aromatics of 1.5 ormore, and a weight ratio of aliphatic sulfur to total sulfur of 0.2 ormore.

Embodiment 7. The resid-containing fraction or fuel composition of anyof the above Embodiments, wherein the resid-containing fractioncomprises a weight ratio of basic nitrogen to total nitrogen of 0.2 ormore; or wherein the resid-containing fraction comprises 5.0 wppm ormore of sodium; or wherein the resid-containing fraction comprises 10wppm or more of calcium; or a combination of two or more thereof.

Embodiment 8. The resid-containing fraction or fuel composition of anyof the above Embodiments, wherein the resid-containing fractioncomprises a) an n-heptane insolubles content of 0.1 wt % or less, b) adensity at 15° C. of 920 kg/m³ or less, c) a naphthenes content of 30 wt% or more, d) a micro carbon residue content of 2.5 wt % or less, e) acombination of two or more of a)-d), or f) a combination of three ormore of a)-d).

Embodiment 9. The resid-containing fraction or fuel composition of anyof the above Embodiments, wherein the resid-containing fractioncomprises a molar ratio of hydrogen to carbon of 1.80 or more, orwherein the resid-containing fraction comprises an energy content of42.0 MJ/kg or more.

Embodiment 10. The resid-containing fraction or fuel composition of anyof the above Embodiments, wherein the resid-containing fractioncomprises a kinematic viscosity at 50° C. of 40 cSt to 120 cSt, orwherein the resid-containing fraction comprises a sulfur content of 0.1wt % or less, or a combination thereof.

Embodiment 11. The resid-containing fraction or fuel composition of anyof the above Embodiments, wherein the resid-containing fractioncomprises a T95 distillation point of 550° C. or more, or wherein theresid-containing fraction comprises a final boiling point of 600° C. ormore, or wherein the resid-containing fraction comprises a T10distillation point of 350° C. or more, or a combination thereof.

Embodiment 12. The resid-containing fraction or fuel composition of anyof the above Embodiments, wherein the resid-containing fractioncomprises a resid-containing fraction derived from a shale oil.

Embodiment 13. Use of a composition comprising a resid-containingfraction or a fuel composition according to any of the above Embodimentsas a fuel in an engine, a furnace, a burner, a combustion device, or acombination thereof.

Embodiment 14. Use of the composition of Embodiment 13, wherein theresid-containing fraction comprises a fraction that has not been exposedto hydroprocessing conditions.

Embodiment 15. A method for forming a resid-containing fraction,comprising: fractionating a whole crude or crude fraction to form aresid-containing fraction according to any of Embodiments 1, 2, or 5-10.

While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For this reason, then, reference shouldbe made solely to the appended claims for purposes of determining thetrue scope of the present invention.

1-20. (canceled)
 21. A resid-containing fraction comprising a T90distillation point of 550° C. or more, a kinematic viscosity at 50° C.of 40 cSt to 180 cSt, a sulfur content of 0.2 wt % or less, and a BMCIof 40 or less.
 22. The resid-containing fraction of claim 21, whereinthe resid-containing fraction comprises a weight ratio of naphthenes toaromatics of 1.5 or more.
 23. The resid-containing fraction of claim 21,wherein the resid-containing fraction comprises a weight ratio of basicnitrogen to total nitrogen of 0.2 or more; or wherein theresid-containing fraction comprises 5.0 wppm or more of sodium; orwherein the resid-containing fraction comprises 10 wppm or more ofcalcium; or a combination of two or more thereof.
 24. Theresid-containing fraction of claim 21, wherein the resid-containingfraction comprises a flash point of 120° C. or more.
 25. Theresid-containing fraction of claim 21, wherein the resid-containingfraction comprises a) an n-heptane insolubles content of 0.1 wt % orless, b) a density at 15° C. of 920 kg/m³ or less, c) a naphthenescontent of 30 wt % or more, d) a micro carbon residue content of 2.5 wt% or less, e) a combination of two or more of a)-d), or f) a combinationof three or more of a)-d).
 26. The resid-containing fraction of claim21, wherein the resid-containing fraction comprises a molar ratio ofhydrogen to carbon of 1.80 or more, or wherein the resid-containingfraction comprises an energy content of 42.0 MJ/kg or more.
 27. Theresid-containing fraction of claim 21, wherein the resid-containingfraction comprises a kinematic viscosity at 50° C. of 40 cSt to 120 cSt,or wherein the resid-containing fraction comprises a sulfur content of0.1 wt % or less, or a combination thereof.
 28. The resid-containingfraction of claim 21, wherein the resid-containing fraction comprises aT95 distillation point of 550° C. or more, or wherein theresid-containing fraction comprises a final boiling point of 600° C. ormore, or wherein the resid-containing fraction comprises a T10distillation point of 350° C. or more, or a combination thereof.
 29. Theresid-containing fraction of claim 21, wherein the resid-containingfraction comprises a resid-containing fraction derived from a shale oil.30. The resid-containing fraction of claim 21, wherein theresid-containing fraction is used as a fuel in an engine, a furnace, aburner, a combustion device, or a combination thereof.
 31. Theresid-containing fraction of claim 21, wherein the resid-containingfraction has not been exposed to hydroprocessing conditions.
 32. A fuelcomposition comprising 5 vol % to 60 vol % of a distillate fraction and40 vol % to 95 vol % of a resid-containing fraction, theresid-containing fraction comprising a T90 distillation point of 550° C.or more, a kinematic viscosity at 50° C. of 40 cSt to 180 cSt, a sulfurcontent of 0.2 wt % or less, and a BMCI of 40 or less.
 33. The fuelcomposition of claim 32, wherein the distillate fraction comprises arenewable distillate fraction.
 34. The fuel composition of claim 33,wherein the renewable distillate fraction comprises one or more ofbiodiesel, fatty acid alkyl ester, and hydrotreated vegetable oil; orwherein the renewable distillate comprises a distillate made, processedor a combination thereof using a renewable energy source; or wherein therenewable distillate comprises a distillate formed from processing ofbiologically derived waste, or a combination thereof.
 35. The fuelcomposition of claim 32, wherein the fuel composition comprises a pourpoint of 30° C. or less.
 36. A method for forming a resid-containingfraction, comprising: fractionating a whole crude or crude fraction toform a resid-containing fraction comprising a T90 distillation point of550° C. or more, a kinematic viscosity at 50° C. of 40 cSt to 180 cSt, asulfur content of 0.2 wt % or less, and a BMCI of 40 or less.
 37. Themethod of claim 36, wherein the resid-containing fraction is formedwithout exposing the resid-containing fraction to hydroprocessingconditions.
 38. The method of claim 36, wherein the resid-containingfraction comprises a weight ratio of naphthenes to aromatics of 1.5 ormore.
 39. The method of claim 36, wherein the resid-containing fractioncomprises a weight ratio of basic nitrogen to total nitrogen of 0.2 ormore; or wherein the resid-containing fraction comprises 5.0 wppm ormore of sodium; or wherein the resid-containing fraction comprises 10wppm or more of calcium; or a combination of two or more thereof. 40.The method of claim 36, wherein the resid-containing fraction comprisesa flash point of 120° C. or more.
 41. A resid-containing fractioncomprising a micro carbon residue content of 2.5 wt % or less, akinematic viscosity at 50° C. of 40 cSt to 180 cSt, a sulfur content of0.2 wt % or less, and a BMCI of 40 or less.
 42. The resid-containingfraction of claim 41, wherein the resid-containing fraction comprises aweight ratio of naphthenes to aromatics of 1.5 or more.
 43. Theresid-containing fraction of claim 41, wherein the resid-containingfraction comprises a weight ratio of basic nitrogen to total nitrogen of0.2 or more; or wherein the resid-containing fraction comprises 5.0 wppmor more of sodium; or wherein the resid-containing fraction comprises 10wppm or more of calcium; or a combination of two or more thereof. 44.The resid-containing fraction of claim 41, wherein the resid-containingfraction comprises a flash point of 120° C. or more.
 45. Theresid-containing fraction of claim 21, wherein the resid-containingfraction comprises a) an n-heptane insolubles content of 0.1 wt % orless, b) a density at 15° C. of 920 kg/m³ or less, c) a naphthenescontent of 30 wt % or more, d) a T90 distillation point of 550° C. ormore, e) a combination of two or more of a)-d), or f) a combination ofthree or more of a)-d).
 46. The resid-containing fraction of claim 41,wherein the resid-containing fraction comprises a molar ratio ofhydrogen to carbon of 1.80 or more, or wherein the resid-containingfraction comprises an energy content of 42.0 MJ/kg or more.
 47. Theresid-containing fraction of claim 41, wherein the resid-containingfraction comprises a kinematic viscosity at 50° C. of 40 cSt to 120 cSt,or wherein the resid-containing fraction comprises a sulfur content of0.1 wt % or less, or a combination thereof.
 48. The resid-containingfraction of claim 41, wherein the resid-containing fraction comprises aT95 distillation point of 550° C. or more, or wherein theresid-containing fraction comprises a final boiling point of 600° C. ormore, or wherein the resid-containing fraction comprises a T10distillation point of 350° C. or more, or a combination thereof.
 49. Theresid-containing fraction of claim 41, wherein the resid-containingfraction comprises a resid-containing fraction derived from a shale oil.